CN102498138B - Resin precursor composition and resin obtained by photocuring same - Google Patents

Resin precursor composition and resin obtained by photocuring same Download PDF

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CN102498138B
CN102498138B CN201080041022.2A CN201080041022A CN102498138B CN 102498138 B CN102498138 B CN 102498138B CN 201080041022 A CN201080041022 A CN 201080041022A CN 102498138 B CN102498138 B CN 102498138B
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methyl
acrylate
hydrogen atom
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CN102498138A (en
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宫川晶子
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Nikon Corp
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Nikon Corp
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/22—Esters containing halogen
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics

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  • Health & Medical Sciences (AREA)
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  • Polymers & Plastics (AREA)
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Abstract

Disclosed is a resin precursor composition comprising a bifunctional (meth)acrylate containing fluorine atom, a bifunctional (meth)acrylate having a fluorene structure and a photopolymerization initiator, which is protected from the formation of deposits during storage. Also disclosed is a resin of the same. Specifically disclosed is a resin precursor composition which comprises a bifunctional fluorinated (meth)acrylate [component (A)], a (meth)acrylate having a fluorene structure [component (B)] and a photopolymerization initiator [component (C)], wherein said component (B) comprises a bifunctional (meth)acrylate having a fluorene structure (b-1) and a monofunctional (meth)acrylate having a fluorene structure (b-2) at a molar ratio (b-1):(b-2) of 90:10 to 70:30.

Description

The resin of resin precursor composition and its photocuring
Technical field
The present invention relates to the resin of resin precursor composition and its photocuring.In more detail, light-cured type (methyl) the acrylic resin precursor composition of attachment multi-layered type diffraction optical element purposes etc. and the resin of its photocuring is related to.
Background technology
2 the optics close attachment formed by optical material together, their interface forms the attachment multi-layered type diffraction optical element of diffraction grating, has the following advantages: use wavelength region can accelerate, and then easily make grating and grating-alignment position.
This attachment multi-layered type diffraction optical element, as such as described in patent documentation 1, need following characteristic: the optical characteristics of 1 parts in 2 opticses in clamping diffraction optics face is relativity high-refractivity and low-dispersion, and the optical characteristics of another parts is the dispersion of relativity low-refraction height.
As the optical material of this low-refraction height dispersion, constantly research and develop the low-refraction height dispersion resin of light weight and bulk excellence in recent years.As this resin, ultraviolet curable resin receives publicity, such as, by using the acrylate and/or methacrylic ester (hereinafter referred to as " (methyl) acrylate ") in molecule with the difunctionality of fluorine atom and (methyl) acrylate with fluorene structured difunctionality, can form the optics be made up of the resin of low-refraction height dispersion of homogeneous, this is disclosed in patent documentation 2.
Prior art document
Patent documentation
Patent documentation 1: Japanese Unexamined Patent Publication 9-127322 publication
Patent documentation 2: International Publication No. 2006/068137 brochure
Summary of the invention
The problem that invention will solve
But containing being with (methyl) acrylate of the difunctionality of fluorine atom, there is (methyl) acrylate of fluorene structured difunctionality and the existing resin precursor composition of Photoepolymerizationinitiater initiater, sometimes in preservation, produce precipitate.Resin precursor composition containing precipitate needs by heating, this precipitate to be dissolved again before use, so can increase cost when manufacturing optical material etc.In addition, the composition deterioration in resin precursor composition may be made by this heating.
The present invention completes in view of above-mentioned present situation, its problem is to provide and suppresses to produce precipitate in preservation, the resin precursor composition of (methyl) acrylate of the difunctionality containing band fluorine atom, (methyl) acrylate with fluorene structured difunctionality and Photoepolymerizationinitiater initiater and this resin.Solve the method for problem
In order to solve above-mentioned problem, the present invention includes following scheme.
(1). a kind of resin precursor composition, it contains following A composition, B component and C composition,
A composition: difunctionality fluorinated acrylate and/or difunctionality fluorine-containing methacrylate;
B component: there is fluorene structured acrylate and/or there is fluorene structured methacrylic ester;
C composition: Photoepolymerizationinitiater initiater;
Above-mentioned B component contains: there is fluorene structured difunctionality acrylate and/or have fluorene structured difunctionality methacrylic ester (b-1) and, there is fluorene structured single functionality acrylate and/or there is fluorene structured single functionality methacrylic ester (b-2), and their molar ratio is (b-1): (b-2)=90: 10 ~ 70: 30.
(2). the resin precursor composition as described in above-mentioned (1), above-mentioned A composition is the compound shown in following general formula (a-1),
In formula, R 21and R 22separately represent hydrogen atom or methyl, x is the integer of 1 ~ 2, and Y represents perfluoroalkyl or the-(CF of carbonatoms 2 ~ 12 2-O-CF 2) z-, above-mentioned z is the integer of 1 ~ 4.
(3). the resin precursor composition as described in above-mentioned (1) or (2), above-mentioned (b-1) is the compound shown in following general formula (b-1-1) and/or the compound shown in following general formula (b-1-2)
In formula, R 1and R 2separately represent hydrogen atom or methyl, R 3and R 4separately represent hydrogen atom, methyl or ethyl, R 9, R 10, R 11and R 12separately represent the phenyl that the alkyl of hydrogen atom, fluorine atom, carbonatoms 1 ~ 6 or hydrogen atom can be replaced by the alkyl of fluorine atom or carbonatoms 1 ~ 6, n1 and n2 separately represents the integer of 0 ~ 3;
In formula, R 5and R 6separately represent hydrogen atom or methyl, R 13, R 14, R 15and R 16separately represent the phenyl that the alkyl of hydrogen atom, fluorine atom, carbonatoms 1 ~ 6 or hydrogen atom can be replaced by the alkyl of fluorine atom or carbonatoms 1 ~ 6, n3 and n4 separately represents the integer of 1 ~ 3.
(4). the resin precursor composition as described in any one of above-mentioned (1) ~ (3), above-mentioned (b-2) is the compound shown in following general formula (b-2-1),
In formula, R 7represent hydrogen atom or methyl, R 8represent straight-chain or the branched-chain alkyl of hydrogen atom or carbonatoms 1 ~ 6, R 17, R 18, R 19and R 20separately represent the phenyl that the alkyl of hydrogen atom, fluorine atom, carbonatoms 1 ~ 6 or hydrogen atom can be replaced by the alkyl of fluorine atom or carbonatoms 1 ~ 6, n5 and n6 separately represents the integer of 0 ~ 10.
(5). the resin precursor composition as described in any one of above-mentioned (1) ~ (4), is characterized in that, is attachment multi-layered type diffraction optical element resin precursor composition.
(6). a kind of photocurable resin, is obtained by the resin precursor composition photocuring described in any one of above-mentioned (1) ~ (5).
(7). the resin as described in above-mentioned (6), refractive index n d is less than 1.54, mean dispersion (n f-n c) be more than 0.0145.
(8). a kind of resin precursor composition, it contains following A composition, B component and C composition,
A composition: difunctionality fluorinated acrylate and/or difunctionality fluorine-containing methacrylate;
B component: there is fluorene structured acrylate and/or there is fluorene structured methacrylic ester;
C composition: Photoepolymerizationinitiater initiater,
Above-mentioned B component is made up of the fluorene structured acrylate that has with fluorene structured acrylate and single functionality of difunctionality.
Invention effect
Resin precursor composition of the present invention, can suppress to produce precipitate in it is preserved, so do not need composition to carry out removing the operation of precipitate before use.In addition, the low-refraction of homogeneous, the resin layer of high dispersion can be formed by photocurable resin of the present invention.
Embodiment
Resin precursor composition of the present invention contains: difunctionality fluorinated acrylate and/or difunctionality fluorine-containing methacrylate (the application is called hereinafter sometimes " difunctionality fluorine-containing (methyl) acrylate ") (A composition), there is fluorene structured acrylate and/or there is fluorene structured methacrylic ester (the application is called hereinafter sometimes " having fluorene structured (methyl) acrylate ") (B component), and Photoepolymerizationinitiater initiater (C composition).
Irradiate light to above-mentioned resin precursor composition, by the effect of above-mentioned C composition, the resin be polymerized by above-mentioned A composition and above-mentioned B component will be obtained.
In resin precursor composition of the present invention, when above-mentioned A composition many containing quantitative change, then the specific refractory power of this resin will step-down, but dispersion degree step-down.This external above-mentioned B component containing quantitative change many time, then the dispersion degree of this resin will become large, but specific refractory power uprises.
Here, the optical characteristics of the low-refraction height dispersion of adhering to multi-layered type diffraction optical element is suitable in order to make the resin obtained by resin precursor composition of the present invention obtain, the content of the above-mentioned A composition in preferred above-mentioned resin precursor composition is below more than 10 quality % 80 quality %, and the content of the above-mentioned B component in preferred above-mentioned resin precursor composition is below more than 10 quality % 80 quality %.In addition, the content of the above-mentioned C composition in preferred above-mentioned resin precursor composition is below more than 0.1 quality % 5 quality %.
Hereinafter be specifically described to above-mentioned A composition, B component and the C composition in resin precursor composition of the present invention.
<A composition >
In resin precursor composition of the present invention, A composition is one kind or two or more difunctionality fluorine-containing (methyl) acrylate.As this difunctionality fluorine-containing (methyl) acrylate, as long as A composition can form (methyl) acrylic resin with B component copolymerization, be not particularly limited, the such as compound shown in following general formula (a-1) is preferred in this resin of optical characteristics obtaining the dispersion of low-refraction height.
[in formula, R 21and R 22separately represent hydrogen atom or methyl, x represents the integer of 1 ~ 2, Y represent carbonatoms 2 ~ 12 perfluoroalkyl or ,-(CF 2-O-CF 2) z-, above-mentioned z represents the integer of 1 ~ 4].
In above-mentioned general formula (a-1), R 21and R 22separately represent hydrogen atom or methyl.
In above-mentioned general formula (a-1), x is the integer of 1 ~ 2, because the optical characteristics of this resin is excellent, so preferably 1.Multiple x in above-mentioned general formula (a-1), both can be identical, also can be different.
In above-mentioned general formula (a-1), Y is perfluoroalkyl or the-(CF of carbonatoms 2 ~ 12 2-O-CF 2) z-, be preferably the perfluoroalkyl of carbonatoms 2 ~ 12.
When above-mentioned Y is the perfluoroalkyl of carbonatoms 2 ~ 12, as its carbonatoms, excellent from the viewpoint of the optical characteristics of this resin, be preferably 2 ~ 8, be more preferably 2 ~ 6, most preferably be 3 ~ 5.
When above-mentioned Y is-(CF 2-O-CF 2) zin-time, z is the integer of 1 ~ 4.
Consider from easily obtaining aspect and excellent compatibility aspect, above-mentioned z is preferably 1 ~ 3, is more preferably 1 or 2, most preferably is 1.
As the concrete example of above-mentioned difunctionality fluorine-containing (methyl) acrylate, can 1 be listed, 4-bis-(methyl) acryloxy-2, 2, 3, 3-tetrafluoro butane, 1, 6-bis-(methyl) acryloxy-3, 3, 4, 4-tetrafluoro hexane, 1, 6-bis-(methyl) acryloxy-3, 3, 4, 4-tetrafluoro hexane, 1, 6-bis-(methyl) acryloxy-2, 2, 3, 3, 4, 4, 5, 5-octafluoro hexane, 1, 8-bis-(methyl) acryloxy-3, 3, 4, 4, 5, 5, 6, 6-octafluoro octane, 1, 8-bis-(methyl) acryloxy-2, 2, 3, 3, 4, 4, 5, 5, 6, 6, 7, 7-12 fluoro-octane, 1, 9-bis-(methyl) acryloxy-2, 2, 3, 3, 4, 4, 5, 5, 6, 6, 7, 7, 8, 8-ten tetrafluoro nonane, 1, 10-bis-(methyl) acryloxy-2, 2, 3, 3, 4, 4, 5, 5, 6, 6, 7, 7, 8, 8, 9, 9-ten hexafluoro decane, 1, 12-bis-(methyl) acryloxy-2, 2, 3, 3, 4, 4, 5, 5, 6, 6, 7, 7, 8, 8, 9, 9, 10, 10, 11, 11-20 fluorine dodecane etc.
And then ethylene-oxide-modifiedly fluoridize dihydroxyphenyl propane two (methyl) acrylate, epoxy pronane modification fluoridizes dihydroxyphenyl propane two (methyl) acrylate etc. also can use by fluorine-containing as difunctionality (methyl) acrylate.
As the A composition in resin precursor composition of the present invention, both can be made up of a kind of difunctionality fluorine-containing (methyl) acrylate, also can be made up of two or more difunctionality fluorine-containing (methyl) acrylate.
The optical characteristics of the low-refraction height dispersion of adhering to multi-layered type diffraction optical element is suitable in order to make the resin obtained by resin precursor composition of the present invention obtain, the content of the above-mentioned A composition in preferred above-mentioned resin precursor composition is below more than 10 quality % 80 quality %, be more preferably below more than 20 quality % 70 quality %, most preferably be below more than 30 quality % 60 quality %.
<B composition >
Resin precursor composition of the present invention, be characterised in that, B component one kind or two or more has fluorene structured (methyl) acrylate, and containing having fluorene structured difunctionality (methyl) acrylate (b-1) and having fluorene structured single functionality (methyl) acrylate (b-2) in above-mentioned B component, their ratio is (b-1): (b-2)=90: 10 ~ 70: 30 (mol ratio) { namely, (b-1) is the ratio of less than more than 2.33 9.00 relative to the mol ratio of (b-2) }.It should be noted that, above-mentioned scope comprises (b-1): the situation of (b-2)=90: 10 (mol ratio) and (b-1): the situation of (b-2)=70: 30 (mol ratio).
By making above-mentioned B component, namely there is fluorene structured difunctionality (methyl) acrylate and contain (b-1) and (b-2), resin precursor composition of the present invention can be suppressed in preservation process to produce precipitate.Preferably mix with above-mentioned molar ratio.
On the other hand; as the existing resin precursor composition disclosed in patent documentation 2, B component is made up of (b-1) substantially; contain (b-2) hardly { even if contain (b-2) as impurity; the content of (b-2) in B component is mol ratio less than 5% } situation, usually can produce precipitate in resin precursor composition between preservation period.This precipitate can be made again to dissolve due to the resin precursor composition creating this precipitate is carried out heating, so can think, this precipitate is by stating A composition and above-mentioned B component is polymerized.In addition, because its form is crystallite sample, so can infer, this precipitate is separated out by the B component with fluorenes ring skeleton that solubleness is lower.Therefore, present inventor has performed further investigation, found that, by the mixture that to be used in (b-1) using above-mentioned mixed in molar ratio (b-2) as above-mentioned B component, can suppress to produce precipitate in the preservation of this resin precursor composition.Although this mechanism is not yet determined when the application submits to, as a kind of imagination, can think, this precipitate is the crystallite of (b-1), and by adding (b-2), its crystallization is hindered, and has not just separated out.
Excellence point of the present invention not only to suppress the generation of precipitate like this, and the resin obtained by this resin precursor composition has the excellent optical properties such with the low-refraction height dispersion of equal extent in the past.
As above-mentioned (b-1) and (b-2) containing than the scope of (mol ratio), be more preferably 88: 12 ~ 70: 30, more and then be preferably 80: 20 ~ 70: 30, most preferably be 80: 20 ~ 75: 25.It should be noted that, the situation of the end of each scope is also included within the scope of this.
Time more than the lower value in above-mentioned scope, the consistency of each composition in resin precursor composition is good, can prevent gonorrhoea when modulating this resin precursor composition.In addition, time below the higher limit for above-mentioned scope, effect of the present invention can be obtained more fully namely, prevent this resin precursor composition from preservation, producing precipitate.As above-mentioned (b-1), the such as compound shown in following general formula (b-1-1) or the compound shown in following general formula (b-1-2) are preferred in this resin of optical characteristics obtaining the dispersion of low-refraction height.
[in formula, R 1and R 2separately represent hydrogen atom or methyl, R 3and R 4separately represent hydrogen atom, methyl or ethyl, R 9, R 10, R 11and R 12separately represent the phenyl that the alkyl of hydrogen atom, fluorine atom, carbonatoms 1 ~ 6 or hydrogen atom can be replaced by the alkyl of fluorine atom or carbonatoms 1 ~ 6, n1 and n2 separately represents the integer of 0 ~ 3].
[in formula, R 5and R 6separately represent hydrogen atom or methyl, R 13, R 14, R 15and R 16separately represent the phenyl that the alkyl of hydrogen atom, fluorine atom, carbonatoms 1 ~ 6 or hydrogen atom can be replaced by the alkyl of fluorine atom or carbonatoms 1 ~ 6, n3 and n4 separately represents the integer of 1 ~ 3].
In above-mentioned general formula (b-1-1), R 1and R 2separately represent hydrogen atom or methyl.
In above-mentioned general formula (b-1-1), R 3and R 4separately represent hydrogen atom, methyl or ethyl, from the viewpoint of easily obtaining, R 3and R 4be preferably hydrogen atom respectively.
In above-mentioned general formula (b-1-1), R 9, R 10, R 11and R 12separately represent the phenyl that the alkyl of hydrogen atom, fluorine atom, carbonatoms 1 ~ 6 or hydrogen atom can be replaced by the alkyl of fluorine atom or carbonatoms 1 ~ 6.
As the alkyl of above-mentioned carbonatoms 1 ~ 6, can be any one in straight-chain, branched or cyclic alkyl, but from the viewpoint of easily obtaining, preferred straight-chain or branched.
As the alkyl of above-mentioned straight-chain or branched, methyl, ethyl, propyl group, sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl, n-pentyl, isopentyl, neo-pentyl, n-hexyl, isohexyl, new hexyl etc. can be listed, from the viewpoint of easily obtaining, preferable methyl or ethyl.
As cyclic alkyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl etc. can be listed, from the viewpoint of easily obtaining, preferred cyclopentyl or cyclohexyl.
Above-mentioned " phenyl that hydrogen atom is replaced by the alkyl of fluorine atom or carbonatoms 1 ~ 6 " is part or all group replaced by the alkyl of fluorine atom or carbonatoms 1 ~ 6 of the hydrogen atom of phenyl.As the alkyl of this carbonatoms 1 ~ 6, from the viewpoint of easily obtaining, preferable methyl or ethyl.
In above-mentioned general formula (b-1-1), n1 and n2 separately represents the integer of 0 ~ 3.From the hardness of this resin and transparency high, and the excellent aspect of its optical characteristics is considered, preferred n1 and n2 separately represents 0 ~ 2, more preferably 0 or 1, most preferably 1.
In above-mentioned general formula (b-1-2), R 5and R 6separately represent hydrogen atom or methyl.
In above-mentioned general formula (b-1-2), R 13, R 14, R 15and R 16separately represent the phenyl that the alkyl of hydrogen atom, fluorine atom, carbonatoms 1 ~ 6 or hydrogen atom can be replaced by the alkyl of fluorine atom or carbonatoms 1 ~ 6.
To the R in the explanation of these groups and above-mentioned general formula (b-1-1) 9, R 10, R 11and R 12explanation identical.
In above-mentioned general formula (b-1-2), n3 and n4 separately represents the integer of 1 ~ 3.From the hardness of this resin and transparency high, and the excellent aspect of its optical characteristics is considered, preferred n3 and n4 separately represents 1 or 2, most preferably 1.
As (b-1) contained in the B component of resin precursor composition of the present invention, particularly preferably be the compound shown in following chemical formula (b-1-01) ~ (b-1-05) and following chemical formula (b-1-06) ~ (b-1-10).It should be noted that, in the compound shown in following chemical formula (b-1-06) ~ (b-1-10), with above-mentioned R 13and R 14corresponding phenyl separately, both can replace the hydrogen atom at ortho position, the hydrogen atom of position between also can replacing.
As above-mentioned (b-2), the such as compound shown in following general formula (b-2-1) is preferred in this resin of optical characteristics obtaining the dispersion of low-refraction height.
[in formula, R 7represent hydrogen atom or methyl, R 8represent straight-chain or the branched-chain alkyl of hydrogen atom or carbonatoms 1 ~ 6, R 17, R 18, R 19and R 20separately represent the phenyl that the alkyl of hydrogen atom, fluorine atom, carbonatoms 1 ~ 6 or hydrogen atom can be replaced by the alkyl of fluorine atom or carbonatoms 1 ~ 6, n5 and n6 separately represents the integer of 0 ~ 10].
In above-mentioned general formula (b-2-1), R 7represent hydrogen atom or methyl.
In above-mentioned general formula (b-2-1), R 8representing straight-chain or the branched-chain alkyl of hydrogen atom or carbonatoms 1 ~ 6, from the viewpoint of easily obtaining, being preferably hydrogen atom.
As straight-chain or the branched-chain alkyl of above-mentioned carbonatoms 1 ~ 6, methyl, ethyl, propyl group, sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl, n-pentyl, isopentyl, neo-pentyl, n-hexyl, isohexyl, new hexyl etc. can be listed, from the viewpoint of easily obtaining, be preferably methyl or ethyl.
In above-mentioned general formula (b-2-1), R 17, R 18, R 19and R 20separately represent the phenyl that the alkyl of hydrogen atom, fluorine atom, carbonatoms 1 ~ 6 or hydrogen atom can be replaced by the alkyl of fluorine atom or carbonatoms 1 ~ 6.
As the alkyl of above-mentioned carbonatoms 1 ~ 6, can being any one of straight-chain, branched or cyclic alkyl, from the viewpoint of easily obtaining, being preferably straight-chain or branched.
As the alkyl of above-mentioned straight-chain or branched, methyl, ethyl, propyl group, sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl, n-pentyl, isopentyl, neo-pentyl, n-hexyl, isohexyl, new hexyl etc. can be listed, from the viewpoint of easily obtaining, preferable methyl or ethyl.
As above-mentioned cyclic alkyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl etc. can be listed, from the viewpoint of easily obtaining, preferred cyclopentyl or cyclohexyl.
Above-mentioned " phenyl that hydrogen atom can be replaced by the alkyl of fluorine atom or carbonatoms 1 ~ 6 " is part or all group optionally replaced by the alkyl of fluorine atom or carbonatoms 1 ~ 6 of the hydrogen atom of phenyl.As the alkyl of this carbonatoms 1 ~ 6, from the viewpoint of easily obtaining, be preferably methyl or ethyl.
In above-mentioned general formula (b-2-1), n5 and n6 separately represents the integer of 0 ~ 10.From the hardness of this resin and transparency high, and the excellent aspect of its optical characteristics is considered, preferred n5 and n6 separately represents 0 ~ 6, is more preferably 0 ~ 3, most preferably is 1 or 2.
(b-2) that B component as resin precursor composition of the present invention comprises, the particularly preferably compound shown in following chemical formula (b-2-01) ~ (b-2-05) and following chemical formula (b-2-06) ~ (b-2-10).It should be noted that, in the compound shown in following chemical formula (b-2-06) ~ (b-2-10) with above-mentioned R 17and R 18corresponding phenyl separately, both can replace the hydrogen atom at ortho position, the hydrogen atom of position between also can replacing.
Compound shown in above-mentioned general formula (b-1-1), the compound shown in the compound shown in above-mentioned general formula (b-1-2) and above-mentioned general formula (b-2-1) both can use commercially available product, also can use known method to synthesize.
As this synthetic method, can list such as, by there is fluorene skeleton 9,9-two (4-hydroxy phenyl) fluorenes or derivatives thereofs with (methyl) vinylformic acid under the existence of the stoppers such as quinhydrones, carried out the method for esterification by the acid catalyst of methylsulfonic acid etc.
When adopting the method, mainly containing (b-1) and (b-2) in the reaction solution after reaction terminates.Being somebody's turn to do can being regulated by suitable adjusting reaction time containing proportional of (b-1) and (b-2), such as, can be (b-1): (b-2)=90: 10 ~ 70: 30 (mol ratio).This situation, just can obtain (b-1) and (b-2) by the building-up reactions of 1 time, so be the method for the B component preferably obtaining resin precursor composition of the present invention.(b-1) that namely can will be removed the unreacted compound, acid catalyst etc. remained in this reaction solution by purifying and obtain: the reaction solution of (b-2)=90: 10 ~ 70: 30 (mol ratio) is as the solution of the B component of resin precursor composition of the present invention.
The mol ratio of (b-1) and (b-2) in this synthesis reaction solution, can be checked by the column chromatography etc. with UV detector.
It should be noted that, when carrying out building-up reactions with the fully long reaction times in aforesaid building-up reactions, the content of (b-2) becomes less than 5% usually.
When preparing the B component of resin precursor composition of the present invention, both sublimed (b-1) and (b-2) in advance can be prepared with aforementioned proportion mixing, also can be such with aforementioned manner, carrying out synthesis makes (b-1) and (b-2) exist with aforementioned proportion in same reaction solution, utilizes this reaction solution to prepare.
(b-1) in the B component of resin precursor composition of the present invention, both can have fluorene structured difunctionality (methyl) acrylate by a kind to form, also can have fluorene structured difunctionality (methyl) acrylate by two or more and form.
In addition, (b-2) in the B component of resin precursor composition of the present invention both can have fluorene structured single functionality (methyl) acrylate by a kind and form, and also can have fluorene structured single functionality (methyl) acrylate by two or more and form.
The optical characteristics of the low-refraction height dispersion of adhering to multi-layered type diffraction optical element is suitable in order to make the resin obtained by resin precursor composition of the present invention have, the content of the above-mentioned B component in above-mentioned resin precursor composition is preferably below more than 10 quality % 80 quality %, be more preferably below more than 20 quality % 70 quality %, most preferably be below more than 30 quality % 60 quality %.In addition, the content of (b-1) and (b-2) in above-mentioned B component is preferably below more than 80 quality % 100 quality %, is more preferably below more than 90 quality % 100 quality %, can also be 100 quality %.When being in this scope, this resin precursor composition can be fully suppressed to produce precipitate in preservation.
<C composition >
C composition in resin precursor composition of the present invention is Photoepolymerizationinitiater initiater.
As this Photoepolymerizationinitiater initiater, as long as the material of above-mentioned A composition and B component polymerization can be caused by rayed, be not particularly limited, the known Photoepolymerizationinitiater initiater used can be used in the photocuring of resin.
As the light in above-mentioned rayed, suitably can select according to the Photoepolymerizationinitiater initiater used, usually can use visible ray, ultraviolet, electron beam etc.
The content of C composition in resin precursor composition of the present invention, different from the kind of the used kind of C composition and the light of irradiation, usually can carry out in the scope of 0.1 ~ 5.0 quality %.
As concrete C composition, the Photoepolymerizationinitiater initiater of such as methyl phenyl ketone system is reactive excellent, so preferably, wherein α position has the alkyl phenyl ketones of hydroxyl, owing to can suppress this resin xanthochromia, so preferably.Particularly, 1-hydroxy-cyclohexyl-phenyl ketone (イ Le ガ キ ユ ア 184), owing to can suppress the xanthochromia of this resin, so be more preferably.
<D composition >
Except above-mentioned A ~ C composition, in resin precursor composition of the present invention, other composition (D composition) can also be contained.By containing D composition, the hardness of this resin and transparency and optical characteristics can be adjusted to the degree of expectation.
In resin precursor composition of the present invention, the content of D composition is preferably 0 ~ 40 quality %, also can be 0 quality %.
D composition both can be can with the composition of above-mentioned A composition and B component copolymerization, also can not the composition of copolymerization, but excellent from the viewpoint of the optical characteristics of this resin, preferably energy copolymerization.
As concrete D composition, can list such as, single functionality (methyl) acrylate, difunctionality (methyl) acrylate, 3 functionality (methyl) acrylate, 4 functionality (methyl) acrylate etc.
As above-mentioned single functionality (methyl) acrylate, can list such as, (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) butyl acrylate, (methyl) isodecyl acrylate, (methyl) lauryl acrylate, (methyl) tridecyl acrylate, (methyl) aliphatic acrylate, (methyl) stearyl acrylate base ester, (methyl) tert-butyl acrylate, (methyl) 2-EHA, (methyl) vinylformic acid 2-hydroxybutyl, (methyl) vinylformic acid 2-hydroxy methacrylate, (methyl) vinylformic acid 2-hydroxy propyl ester, (methyl) vinylformic acid 3-methoxybutyl, (methyl) vinylformic acid diethylamino ethyl ester, phenoxy group polyoxyethylene glycol (methyl) acrylate, (methyl) vinylformic acid iso stearyl ester, to cumylphenoxy ethylene glycol (methyl) acrylate, (methyl) acrylate, 2-ethylhexyl Trivalin SF (methyl) acrylate, (methyl) acrylate, butoxy ethyl, ethoxydiglycol (methyl) acrylate, dodecyloxy polyoxyethylene glycol (methyl) acrylate, polyoxyethylene glycol (methyl) acrylate, polypropylene glycol (methyl) acrylate, acryloxy polyoxyethylene glycol (methyl) acrylate, octadecane oxygen base polyoxyethylene glycol (methyl) acrylate, octyloxy polyethylene glycol-propylene glycol (methyl) acrylate, poly-(propylene glycol-BDO) (methyl) acrylate, poly-(ethylene glycol-BDO) (methyl) acrylate, methoxy poly (ethylene glycol) (methyl) acrylate, methoxyl group polypropylene glycol (methyl) acrylate, (methyl) benzyl acrylate etc.
As above-mentioned difunctionality (methyl) acrylate, can list such as, 2-ethyl-2-butyl-propylene glycol two (methyl) acrylate, 1, 3-butyleneglycol two (methyl) acrylate, 1, 6-hexylene glycol two (methyl) acrylate, 1, 9-nonanediol two (methyl) acrylate, 1, 10-decanediol two (methyl) acrylate, neopentyl glycol two (methyl) acrylate, dipropylene glycol two (methyl) acrylate, glycerine two (methyl) acrylate, ethylene-oxide-modified neopentyl glycol two (methyl) acrylate, epoxy pronane modification neopentyl glycol two (methyl) acrylate, ethylene-oxide-modified dihydroxyphenyl propane two (methyl) acrylate, epoxy pronane modification dihydroxyphenyl propane two (methyl) acrylate, ethylene oxide propylene oxide modified bisphenol A two (methyl) acrylate, butyl ethyl propylene glycol two (methyl) acrylate etc.
As above-mentioned 3 functionality (methyl) acrylate, can list such as, three (acryloyl-oxyethyl) isocyanuric acid ester, three (methacryloxyethyl) isocyanuric acid ester, epoxychloropropane modified glycerine three (methyl) acrylate, ethylene-oxide-modified glycerine three (methyl) acrylate, epoxy pronane modification glycerine three (methyl) acrylate, caprolactone modification trimethylolpropane tris (methyl) acrylate, ethylene-oxide-modified trimethylolpropane tris (methyl) acrylate, epoxy pronane modification trimethylolpropane tris (methyl) acrylate, tetramethylolmethane three (methyl) acrylate, trimethylolpropane tris (methyl) acrylate etc.
As above-mentioned 4 functionality (methyl) acrylate, can list such as, tetramethylolmethane four (methyl) acrylate, Dipentaerythritol hydroxyl five (methyl) acrylate, two (TriMethylolPropane(TMP)) four (methyl) acrylate etc.
In these D compositions, as single functionality (methyl) acrylate, phenoxy group ethylene glycol (methyl) acrylate, methoxyl group glycol ether (methyl) acrylate, (methyl) benzyl acrylate, methoxyl group tripropylene glycol (methyl) acrylate or as difunctionality (methyl) acrylate, neopentyl glycol two (methyl) acrylate, tripropylene glycol two (methyl) acrylate, the optical characteristics of consistency and this resin is excellent, so preferably.
Resin precursor composition of the present invention is characterised in that, containing above-mentioned A composition, B component and C composition, and the mol ratio of (b-1) and (b-2) in B component is (b-1): (b-2)=90: 10 ~ 70: 30 (mol ratio), described in the same, it can play and suppress precipitate to produce such unusual effect in preservation.
Can think, carrying out photocuring thus the photocurable resin obtained by irradiating light to resin precursor composition of the present invention, is (methyl) acrylic resin of A composition and B component random copolymerization.
Such as, as the preference of resin precursor composition of the present invention, A composition can be listed for the compound shown in above-mentioned general formula (a-1), B component is the resin precursor composition of the compound shown in the compound shown in following chemical formula (b-1-1) and following chemical formula (b-2-1), carrying out photocuring through rayed by this resin precursor composition and the photocurable resin obtained, is the random copolymers of these compounds.The structural unit (A-1-1) of this random copolymers, structural unit (B-1-1) and structural unit (B-2-1) are respectively as shown in following general formula (A-1-1), following general formula (B-1-1) and following general formula (B-2-1).
[in formula, R 21and R 22separately represent hydrogen atom or methyl, x represents the integer of 1 ~ 2, Y represent carbonatoms 2 ~ 12 perfluoroalkyl or ,-(CF 2-O-CF 2) z-, above-mentioned z represents the integer of 1 ~ 4].
[in formula, R 1and R 2separately represent hydrogen atom or methyl, R 3and R 4separately represent hydrogen atom, methyl or ethyl, R 9, R 10, R 11and R 12separately represent the phenyl that the alkyl of hydrogen atom, fluorine atom, carbonatoms 1 ~ 6 or hydrogen atom can be replaced by the alkyl of fluorine atom or carbonatoms 1 ~ 6, n1 and n2 separately represents the integer of 0 ~ 3].
[in formula, R 7represent hydrogen atom or methyl, R 8represent straight-chain or the branched-chain alkyl of hydrogen atom or carbonatoms 1 ~ 6, R 17, R 18, R 19and R 20separately represent the phenyl that the alkyl of hydrogen atom, fluorine atom, carbonatoms 1 ~ 6 or hydrogen atom can be replaced by the alkyl of fluorine atom or carbonatoms 1 ~ 6, n5 and n6 separately represents the integer of 0 ~ 10].
About the R in above-mentioned general formula (A-1-1) 21, R 22, x, Y and z explanation, with the R in aforementioned formula (a-1) 21, R 22, x, Y and z explanation same.
About the R in above-mentioned general formula (B-1-1) 1, R 2, R 3, R 4, R 9, R 10, R 11, R 12, n1 and n2 explanation, with the R in aforementioned formula (b-1-1) 1, R 2, R 3, R 4, R 9, R 10, R 11, R 12, n1 and n2 explanation same.
About the R in above-mentioned general formula (B-2-1) 5, R 6, R 13, R 14, R 15, R 16, n3 and n4 explanation, with the R in above-mentioned general formula (b-2-1) 5, R 6, R 13, R 14, R 15, R 16, n3 and n4 explanation same.
The photocurable resin be light-cured into resin precursor composition irradiation light of the present invention, has the optical characteristics that the dispersion of low-refraction height is such.
Such as, be below more than 10 quality % 80 quality % by making the content of the A composition in above-mentioned resin precursor composition, make the content of the B component in above-mentioned resin precursor composition be below more than 10 quality % 80 quality %, the refractive index n of the resin after photocuring can be made like this dbe less than 1.54, the mean dispersion (n of this resin f-n c) be more than 0.0145.
The resin with the optical characteristics of this low-refraction height dispersion is suitable as resin used for optical elements, is particularly suitable as attachment multi-layered type diffraction optical element resin.Here attachment multi-layered type diffraction optical element is instigated the high-refractivity and low-dispersion resin with the such optical characteristics of high-refractivity and low-dispersion and has the low-refraction height dispersion resin close attachment of the such optical characteristics of low-refraction height dispersion, optical element stacked together.It should be noted that, the interface of high-refractivity and low-dispersion resin and low-refraction height dispersion resin is formed embossing pattern (surface undulation pattern).Embossing pattern both can be zigzag fashion, also can be rectangular shape.Multiple zigzag fashion, multiple rectangular shape are formed on the surface.And the interface shape of high-refractivity and low-dispersion resin has the shape contrary with the interface shape of low-refraction height dispersion resin.It should be noted that, the grating height of saw tooth pattern is set according to the value (hereinafter referred to as " refringence ") of the specific refractory power of high-refractivity and low-dispersion resin under certain wavelength used in wavelength domain and the specific refractivity of low-refraction height dispersion resin and using the determined height of ratio between certain wavelength in wavelength domain.Be preferably, when the product of the grating height of refringence and saw tooth pattern is the integral multiple of certain wavelength used in wavelength domain, the diffraction efficiency of the diffraction number of times of regulation uprises.The phase differential of the light produced by the embossing pattern at the interface of this high-refractivity and low-dispersion resin and low-refraction height dispersion resin, even if wavelength change does not have too large change yet.Therefore, resin precursor composition of the present invention is suitable as attachment multi-layered type diffraction optical element resin precursor composition.
By irradiating light to above-mentioned attachment multi-layered type diffraction optical element resin precursor composition, carry out photocuring and the attachment multi-layered type diffraction optical element resin that obtains, be suitable as the material of attachment multi-layered type diffraction optical element.The optical characteristics of this attachment multi-layered type diffraction optical element is described below.
Attachment multi-layered type diffraction optical element, the optical characteristics of the optics in clamping diffraction optics face requires that relativity ground is high-refractivity and low-dispersion and the dispersion of low-refraction height.Here as the optical material of high-refractivity and low-dispersion, a lot of situation uses low melting glass.In this situation, by using glass template to form diffraction surfaces on glass, then at this diffraction surfaces superimposed layer photocurable resin of the present invention, attachment multi-layered type diffraction optical element just can be made.As one of low melting glass used in this purposes, there is K-PSK60 (field optics ガ ラ ス Inc. is lived by Co., Ltd.).
With wavelength X 0lower m 0secondary diffraction efficiency is the mode optimized grating height d of 100% 0, as the λ of the material by high-refractivity and low-dispersion and the dispersion of low-refraction height 0under specific refractory power be set to n respectively 1(λ 0), n 2 (λ 0)time, with formula { n 1 (λ 0)-n 2 (λ 0)} × d 0=m 0× d 0represent.Namely, grating height d 0inversely proportional with the refringence of the material of high-refractivity and low-dispersion and the material of low-refraction height dispersion.
In addition, when by the diffraction efficiency of m time m, at setting a={ (n 1-1) d-(n 2-1) during d}/λ, with formula η m={ sin (a-m) π/(a-m) π } 2represent.
In general, diffraction optical element, in order to reduce field angle dependency, and wishes that grating height is lower, in order to reduce flash of light, and wish diffraction efficiency just and use wavelength region may all higher.Here, when by K-PSK60 and photocurable resin of the present invention (such as, n d=1.54, n f-n c=1.5502-1.5357=0.0145) when combining, the attachment multi-layered type diffraction optical element with excellent diffraction efficiency can be realized, its grating height is low reaches 11.55 μm, in addition diffraction efficiency for being 95%, being 100% under d line (wavelength 587.56nm), being 98% under C line (wavelength 656.27nm) under F line (wavelength 486.13nm), and diffraction efficiency is more than 95% throughout visible region.
Therefore, when resin precursor composition of the present invention being used as attachment multi-layered type diffraction optical element resin precursor composition, the refractive index n after preferred light solidification dbe less than 1.54, the mean dispersion (n of this resin f-n c) be more than 0.0145.Now, another optics preferred index n in multi-layered type diffraction optical element is adhered to dbe more than 1.55, the mean dispersion (n of this resin f-n c) be less than 0.013.
The concrete manufacture method with the attachment multi-layered type diffraction optical element of this optical characteristics is known, has disclosed the manufacture method of paragraph [0055] ~ [0057] of such as patent documentation 2.
Embodiment
Further illustrate the present invention below by embodiment, but the present invention does not limit by these examples.
[embodiment 1 ~ 12, comparative example 1 ~ 6]
By each composition mixing shown in table 1, dissolve, prepare resin precursor composition.(b-1) in this B component is as shown in table 1 relative to the mol ratio of (b-2).
Table 1
Numeric representation use level (mass parts) in table 1, in [].In addition, the symbol implication in table 1 is as follows respectively.
(A)-1:2,2,3,3,4,4,5,5-octafluoro hexane-1,6-diacrylate
(B)-1: the mixture that the compound shown in the compound shown in above-mentioned chemical formula (b-1-02) and above-mentioned chemical formula (b-2-02) exists with 95: 5 (mol ratios)
(B)-2: the mixture that the compound shown in the compound shown in above-mentioned chemical formula (b-1-02) and above-mentioned chemical formula (b-2-02) exists with 90: 10 (mol ratios)
(B)-3: the mixture that the compound shown in the compound shown in above-mentioned chemical formula (b-1-02) and above-mentioned chemical formula (b-2-02) exists with 88: 12 (mol ratios)
(B)-4: the mixture that the compound shown in the compound shown in above-mentioned chemical formula (b-1-02) and above-mentioned chemical formula (b-2-02) exists with 79: 21 (mol ratios)
(B)-5: the mixture that the compound shown in the compound shown in above-mentioned chemical formula (b-1-02) and above-mentioned chemical formula (b-2-02) exists with 76: 24 (mol ratios)
(B)-6: the mixture that the compound shown in the compound shown in above-mentioned chemical formula (b-1-02) and above-mentioned chemical formula (b-2-02) exists with 55: 45 (mol ratios)
(C)-1: イ Le ガ キ ユ ア 184 (チ バ ス ペ シ ヤ Le テ イ mono-ケ ミ カ Le ズ Inc.)
(D)-1: phenoxy group EDIA
(D)-2: methoxyl group polypropylene glycol acrylate
It should be noted that, the B component shown in symbol of above-mentioned (B)-1 ~ (B)-6, can by by two for 9,9-(4-ethoxyl phenenyl) fluorenes and vinylformic acid under the existence of quinhydrones, the synthetic method of being carried out esterification by acid catalyst methylsulfonic acid is obtained.Now can pass through suitable adjusting reaction time, what make (b-1) and (b-2) becomes desired mol ratio containing proportional.This mol ratio can be confirmed by the column chromatography analysis reaction solution with UV detector.From reaction solution, remove other composition beyond (b-1) and (b-2), the B component of gained is used for preparing above-mentioned resin precursor composition.
Each resin precursor composition of gained is injected in 4 lucifuge vials respectively, at room temperature preserves, investigate and produce with or without precipitate.Result is as shown in table 2.
Table 2
In table 2, "×" represents and occurs separating out, and " Δ " represents the precipitation occurring denier, and "○" indicates without precipitation.There is the number of the lucifuge vial of the precipitation of precipitation or denier in the numeric representation in addition in ().It should be noted that, in comparative example 2,4,6, after preparation resin precursor composition, occur gonorrhoea at once, the presence or absence of precipitate can not be evaluated.
In addition, in each resin precursor composition made, except the comparative example 2,4,6 bleaching turbid, the resin precursor composition to embodiment 1 ~ 12 and comparative example 1,3,5 irradiates 8000mJ/cm 2ultraviolet (wavelength: 365nm) carry out photocuring, obtain photocurable resin.Measure the specific refractory power (22.5 DEG C) of each photocurable resin of gained, the refractive index n of all photocurable resin of result dbe 1.528, its mean dispersion (n f-n c) be 0.0150.
Can be confirmed by above result, even if the resin precursor composition of embodiment involved in the present invention 1 ~ 12 does not have precipitate to produce after preservation 3 week yet, even if the resin precursor composition of embodiment 2,3,4,6,7,8,10,11,12 does not have precipitate to produce after preservation 5 week yet, even if the resin precursor composition of embodiment 3,4,7,8,11,12 does not have precipitate to produce after preserving half a year yet.On the other hand, the resin precursor composition of comparative example 1,3,5 produces precipitate all without any exception, all after preservation 3 week.
In addition, the photocurable resin that resin precursor composition irradiation ultraviolet radiation to embodiment 1 ~ 12 involved in the present invention carries out photocuring and obtains, all there is the excellent optical properties of low-refraction height dispersion, be suitable as the resin forming attachment multi-layered type diffraction optical element.

Claims (6)

1. a resin precursor composition, it contains following A composition, B component and C composition,
A composition: difunctionality fluorinated acrylate and/or difunctionality fluorine-containing methacrylate;
B component: there is fluorene structured acrylate and/or there is fluorene structured methacrylic ester;
C composition: Photoepolymerizationinitiater initiater;
Above-mentioned B component contains following b-1 composition and b-2 composition:
B-1 composition: there is fluorene structured difunctionality acrylate and/or there is fluorene structured difunctionality methacrylic ester,
B-2 composition: there is fluorene structured single functionality acrylate and/or there is fluorene structured single functionality methacrylic ester,
And their molar ratio is (b-1): (b-2)=90:10 ~ 70:30,
Above-mentioned b-1 composition is the compound shown in following general formula (b-1-1) and/or the compound shown in following general formula (b-1-2),
In formula, R 1and R 2separately represent hydrogen atom or methyl, R 3and R 4separately represent hydrogen atom, methyl or ethyl, R 9, R 10, R 11and R 12separately represent the phenyl that the alkyl of hydrogen atom, fluorine atom, carbonatoms 1 ~ 6 or hydrogen atom can be replaced by the alkyl of fluorine atom or carbonatoms 1 ~ 6, n1 and n2 separately represents the integer of 0 ~ 3;
In formula, R 5and R 6separately represent hydrogen atom or methyl, R 13, R 14, R 15and R 16separately represent the phenyl that the alkyl of hydrogen atom, fluorine atom, carbonatoms 1 ~ 6 or hydrogen atom can be replaced by the alkyl of fluorine atom or carbonatoms 1 ~ 6, n3 and n4 separately represents the integer of 1 ~ 3,
Above-mentioned b-2 composition is the compound shown in following general formula (b-2-1),
In formula, R 7represent hydrogen atom or methyl, R 8represent straight-chain or the branched-chain alkyl of hydrogen atom or carbonatoms 1 ~ 6, R 17, R 18, R 19and R 20separately represent the phenyl that the alkyl of hydrogen atom, fluorine atom, carbonatoms 1 ~ 6 or hydrogen atom can be replaced by the alkyl of fluorine atom or carbonatoms 1 ~ 6, n5 and n6 separately represents the integer of 0 ~ 10.
2. resin precursor composition as claimed in claim 1, above-mentioned A composition is the compound shown in following general formula (a-1),
In formula, R 21and R 22separately represent hydrogen atom or methyl, x is the integer of 1 ~ 2, and Y represents perfluoroalkyl or the-(CF of carbonatoms 2 ~ 12 2-O-CF 2) z-, above-mentioned z is the integer of 1 ~ 4.
3. resin precursor composition as claimed in claim 1, is characterized in that, is attachment multi-layered type diffraction optical element resin precursor composition.
4. resin precursor composition as claimed in claim 1, described B component is made up of described b-1 composition and described b-2 composition, and described b-1 composition is have fluorene structured difunctionality acrylate, and described b-2 composition is have fluorene structured single functionality acrylate.
5. a photocurable resin, is obtained by resin precursor composition photocuring according to claim 1.
6. photocurable resin as claimed in claim 5, refractive index n dbe less than 1.54, mean dispersion (n f-n c) be more than 0.0145.
CN201080041022.2A 2009-07-22 2010-07-20 Resin precursor composition and resin obtained by photocuring same Active CN102498138B (en)

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